CN102827825B - Immobilized lipase catalyst for preparing biodiesel and application of immobilized lipase catalyst - Google Patents
Immobilized lipase catalyst for preparing biodiesel and application of immobilized lipase catalyst Download PDFInfo
- Publication number
- CN102827825B CN102827825B CN201210309958.XA CN201210309958A CN102827825B CN 102827825 B CN102827825 B CN 102827825B CN 201210309958 A CN201210309958 A CN 201210309958A CN 102827825 B CN102827825 B CN 102827825B
- Authority
- CN
- China
- Prior art keywords
- lipase
- sepiolite
- immobilized
- acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Enzymes And Modification Thereof (AREA)
Abstract
The invention discloses a lipase catalyst immobilized on sepiolite, a preparation method of the lipase catalyst and a method for preparing biodiesel from the catalyst, and belongs to the field of preparation of biodiesel. Dosage of the immobilized lipase catalyst is low, and the immobilized lipase catalyst can be reused by 10 times. In addition, the biodiesel prepared from the catalyst is high in reaction activity and high in reaction speed, reaction conditions are mild relatively, reaction can be carried out under atmospheric pressure at low temperature, and reaction energy consumption and cost can be reduced. Besides, a production process is environment-friendly, an operation process is simple, and erosion to equipment is low.
Description
Technical field
The present invention relates to a kind of for the preparation of immobilized lipase-catalyzed dose of biofuel, its preparation method and utilize it to prepare the method for biofuel, be specifically related to a kind of immobilized on sepiolite lipase-catalyzed dose, its preparation method and utilize the method for described biodiesel, belong to diesel preparation field.
Background technology
According to biofuel association of the U.S. (National Biodiesel Borad in 1992, NBB) definition provided, biofuel (Biodiesel) refers to the clean replacing fuel oil that can be used for self-igniton engine produced with the renewable biological source such as plant, animal grease.Along with petroleum resources are petered out and the deterioration of environment, biofuel is as oil-fired surrogate, have substantially not sulfur-bearing and aromatic hydrocarbons, energy density is high, cetane value is high, lubricity is good, storing and transporting security, anti-knocking property are good, sufficient combustion, can biological degradation, the premium properties such as nontoxic, be that a kind of tool grows a lot eco-friendly large bio-based liquid fuel of potentiality.
The preparation method of biofuel has Physical and chemical method.Physical is simple to operate, but the problems such as the stuck and carbon distribution of sintering (as engine nozzle) in various degree, piston ring in use can occur the product that Physical obtains.Chemical method mainly comprises pyrolysis method and ester-interchange method.Wherein, the quality product that pyrolysis method obtains is better, but preparation process condition harshness (as high temperature), reaction is difficult to control, and product component is complicated, equipment and running cost high, be not thus widely used.And ester-interchange method to be animal-plant oil and short chain alcohol carry out transesterification reaction, generate the fatty acid ester (i.e. biofuel) that relative molecular mass is little.
And the method for preparing biodiesel by ester interchange can be divided into chemical catalysis, enzyme catalysis method and supercritical methanol technology.Chemical catalysis mainly contains acid catalysis and base catalysis, and wherein acid catalysis is to the wide adaptability of raw material, but classical acid Catalytic processes is serious to equipment corrosion, and speed of reaction is slow, energy consumption is large, yield is low; And although the solid acid catalysis in new technology reacts the etching problem solved equipment, active on the low side, speed of reaction is slower.And base catalysis although comparatively surface acidity is high, speed of reaction is high and not etching apparatus, the requirement for raw material is high, can only use lipid acid and the low raw material of water-content.The speed of reaction of Preparation of Biodiesel by Supercritical Method is very high, the strong adaptability to raw material, environmental friendliness, speed of reaction are fast, transformation efficiency is high, but its severe reaction conditions, carry out under needing High Temperature High Pressure, higher to the requirement of equipment.
Enzyme catalysis method is prepared biofuel and is referred to that with lipase be catalyzer, and alcohol and vegetables oil are carried out the process that transesterification reaction generates fatty acid ester.The advantages such as enzyme catalysis method has that glyceride stock suitability is wide, reaction conditions is gentle (30-40 DEG C), alcohol consumption is little, fatty acid ester yield is higher, product is easy to collect and pollution-free.But because a lot of enzyme is strong to the dependency of water, and the activity of alcohol system to enzyme of biofuel Exchange Ester Process also has a certain impact, and causes the catalytic life of enzyme shorter, limits the development of process for preparing biodiesel by enzyme.
In order to solve the loss of enzyme, reduce the catalysis cost of enzyme, immobilized enzyme receives concern, as with kaoline loaded lipase (Production of biodiesel fuel from triglycerides and alcohol using immobilized lipase.Iso M, Chen B, Eguchi M, et al.Journal of Molecular Catalysis B:Enzymatic, 2001,16:53-58); Deng Li etc. have successfully extracted lipase from candida sp from candiyeast fermented liquid, be fixed on textiles, be applied in the transesterification reaction of waste grease and edible oil, deposit in case at organic solvent, the qualified biodiesel oil product of performance (research of Biodiesel Production by Lipase-catalysis, Deng Li etc., biotechnology journal are successfully produced out, 2003,19(1): 97-101); Shah etc. by immobilized for Chromobacterium viscosum on Delite-545, yield (the Shan S of 71% is obtained at 40 DEG C of reaction 8h, Sharma S, Gupta M N.Biodiesel preparation by Lipase-Catalyzed transesterification of Jatropha oil.Energy and Fuels, 2004,18 (1): 154-159); With the material solid supported lipase of silica-based MCF (the material solid supported lipase of silica-based MCF transforms waste cooking oil and produces biofuel, Shen Yu, Journal of Chemical Industry and Engineering, 2012,63(6)) etc.The reaction conditions of process for preparing biodiesel by enzyme is gentle, but expensive due to enzyme, cause cost higher; And the severe reaction conditions of enzyme, easily inactivation, recycling number of times is low.
Therefore, how to develop a kind ofly can repeatedly to reuse, cost is lower, active more stable for the preparation of biofuel lipase-catalyzed dose, is this area technical problem urgently to be resolved hurrily.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of and can repeatedly reuses, cost is lower, active more stable for the preparation of biofuel lipase-catalyzed dose, especially a kind of immobilized lipase-catalyzed dose of preparing biofuel, is specially immobilized for lipase on sepiolite.
Sepiolite is the moisture magnesium silicate clay mineral of a kind of natural fiber, in its structural unit, silicon-oxy tetrahedron and magnesia octahedra mutually alternately, have the transition type feature of stratiform and chain-like structure, its ideal structure formula can be expressed as Si
12o
30mg
8(OH)
4(H
2o)
48H
2o.The special construction of sepiolite determines it and has good physical and chemical performance (i.e. adsorptivity, rheological and catalytic performance) and the advantage such as cheap, and thus application prospect is very extensive.
Sepiolite, as a kind of multi-hole type inorganic polymer material, because it has huge specific surface free energy, can adsorb or cover all kinds of catalyst simple substance or compound.These simple substance and compound can enter sepiolite channel interior, and this point is SiO
2and Al
2o
3incomparable.Secondly, owing to self there is many basic center [MgO in sepiolite
6] and acid sites [SiO
4], after reactant molecule is adsorbed, easily polarization is deformed into activated complex, thus can promote the generation of reaction.Therefore, sepiolite itself has certain katalysis.In actual applications, sepiolite can produce concerted catalysis effect together with catalyzer, improves catalytic effect.Again, special method of modifying can being taked, as adopted the modified method of acid, sepiolite aperture or staple length and concrete catalyst-compatible can be made.In preparation particular type catalyzer, this superiority not available for conventional carriers, provides larger space for we explore new preparation method.In addition, sepiolite carried catalyst, selectivity high with its activity is got well and is had certain thermotolerance and toxin immunity and show superior Practical Performance.
The present invention is immobilized on sepiolite by lipase-catalyzed dose, combine the good adsorptivity of sepiolite, rheological and catalytic performance, serve the effect of synergy after being combined with lipase, immobilized lipase activity on sepiolite is stablized, and can reuse.
Preferably, sepiolite of the present invention is the sepiolite of sour modification, and namely immobilized lipase-catalyzed dose of the present invention is immobilized on the sepiolite of sour modification lipase-catalyzed dose.
Wherein, the combination of any a kind or at least 2 kind of the acid in the sepiolite of described sour modification preferably in hydrochloric acid, sulfuric acid or nitric acid, described combination is hydrochloric acid/sulfuric acid, nitric acid/hydrochloric acid, hydrochloric acid/sulfuric acid/nitric acid etc. such as, preferred from hydrochloric acid and/or sulfuric acid further, further preferred hydrochloric acid.
Natural sepiolite self acidity is extremely weak, carries out acid be modified as with the magnesium ion in different positively charged ions replacement sepiolite skeleton sepiolite.Due to Mg
2+be a weak base, meet weak acid and can generate precipitation and be deposited in the microvoid structure of sepiolite, therefore process acid is at present strong acid (as HNO
3, H
2sO
4and HCl etc.).The treatment mechanism of different strong acid to sepiolite is identical, is H
+replace the Mg in skeleton
2+.Sepiolite becomes two Si-O-H keys through its Si-O-Mg-O-Si key of acid treatment, and namely occurred the structure of " bypassing " state, now internal passages is connected, therefore specific surface area increases.
Once with hydrochloric acid, sepiolite was processed, to investigate the impact of acid on sepiolite structure, result shows, acid treatment makes sepiolite specific surface area be greatly improved, mesopore (acidity of sepiolite and the performance study: the structure of I. modification course and modified product, Jiang Wenbin etc., petroleum journal of 2-5nm is developed into by micropore (<2nm) in aperture, 1994,10 (1): 29-35).
Because sepiolite is acidified, its specific surface area increases, the present invention further by immobilized for lipase on the sepiolite of sour modification, immobilized lipase-catalyzed dose can be made to obtain more stable activity, acidproof, alkaline-resisting, resistance to elevated temperatures is all improved, and can reuse, modify flexibly, thus reduce cost.
Two of object of the present invention is to provide a kind of aforementioned immobilized preparation method of lipase-catalyzed dose on sepiolite, and described method comprises the steps:
(1) sour modification is carried out to sepiolite;
(2) by the sepiolite after immobilized for the lipase sour modification obtained in step (1).
Preferably, sour modification carried out to sepiolite comprise the steps: described in step (1)
(1a) sepiolite is placed in acid to soak;
(1b) by the sepiolite washing after immersion, filter, dry, pulverize, calcination.
Preferably, step (1a) described acid is selected from the combination of any a kind or at least 2 kinds in hydrochloric acid, sulfuric acid or nitric acid, preferred hydrochloric acid and/or sulfuric acid, further preferred hydrochloric acid.It is H with acid that sepiolite is placed in object that acid soaks by the present invention
+replace the Mg in skeleton
2+, open Si-O-Mg-O-Si key and become two Si-O-H keys, be communicated with sepiolite internal passages, increase specific surface area.
Preferably, the concentration of described acid is preferably 0.1-6mol/L, such as 0.2mol/L, 0.45mol/L, 1.2mol/L, 2.6mol/L, 3.61mol/L, 4.52mol/L, 5.68mol/L, 5.84mol/L etc., more preferably 0.4-2.8mol/L.During the concentration > 6mol/L of acid of the present invention, excessive concentration, operation inconvenience, and easily and Si there is side reaction, affect the internal structure of sepiolite, be unfavorable for the stability of follow-up lipase load; And as the concentration < 0.1mol/L of acid, concentration is too low, with Mg
2+sluggish, and easily cause the wasting of resources.
In a preferred embodiment, step of the present invention (1a) described acid is selected from the hydrochloric acid that concentration is 0.1-6mol/L, and preferred concentration is the hydrochloric acid of 0.4-2.8mol/L.
Preferably, step (1a) described sepiolite is the acid that every gram of sepiolite adds 8-70mL with the ratio of acid, the amount of the acid that such as every gram of sepiolite adds is 8.2mL, 9.2mL, 15mL, 22mL, 30.5mL, 39mL, 43mL, 50.7mL, 55mL, 60.4mL, 67mL, 69.2mL etc., and preferably every gram of sepiolite adds the acid of 10-25mL.As the amount < 8mL of the acid that every gram of sepiolite adds, H
+measure less, be not enough to the Mg all replaced in sepiolite
2+, cause the waste of sepiolite resource; As the amount > 70mL of the acid that every gram of sepiolite adds, due to Mg
2+substantially by H
+replace, unnecessary H
+cause waste.
Preferably, step (1a) described soaking temperature is 30-90 DEG C, and such as soaking temperature is 31 DEG C, 34.2 DEG C, 38 DEG C, 45 DEG C, 52 DEG C, 59.3 DEG C, 64 DEG C, 76 DEG C, 82 DEG C, 86.8 DEG C, 89 DEG C etc., preferred 35-75 DEG C; Soak time is 12-30h, and such as soak time is 12.3h, 12.9h, 13.6h, 15.8h, 17.2h, 20.3h, 24h, 27h, 28.1h, 28.8h, 29h, 29.6h etc., preferred 13-25h.
Preferably, step (1b) described washing is for washing with water, and described wet concentration is from deionized water and/or distilled water; Described calcination temperature is preferably 220-280 DEG C, such as 225 DEG C, 238 DEG C, 251 DEG C, 268 DEG C, 274 DEG C, 277 DEG C etc., further preferred 230-250 DEG C, particularly preferably 240 DEG C.
Of the present invention the step of sour modification and the operational condition of each step are carried out to sepiolite, be not limited in above-mentioned condition, above-mentioned each operation is optimum condition of the present invention and step, can meet and the experiment condition of sepiolite acidic treatment all be can be used for the present invention.
As a preferred embodiment of the present invention, sour modification carried out to sepiolite comprise the steps: described in step of the present invention (1)
At 30-90 DEG C, add the hydrochloric acid that concentration is 0.4-2.8mol/L in sepiolite, hydrochloric acid add-on is 10-25mL/ every gram sepiolite, soaks 12-30h; Then use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtain the sepiolite that acid is modified.
Preferably, the lipase described in step of the present invention (2) is immobilized to be comprised the steps:
(2a) lipase is dissolved in buffered soln, mixing, obtains lipase solution;
(2b) in lipase solution, add the sepiolite of the sour modification that step (1) obtains, mixing, carries out immobilized reaction;
(2c) reaction product is cleaned, filter, dry, obtain immobilized immobilized lipase on sepiolite; The immobilized lipase normal temperature of gained is preserved.
The object of step (2a) described damping fluid is normal ph in order to maintain lipase and normal physiological context, and play the effect ensureing lipase activity, the selection of damping fluid is operation well-known to those skilled in the art.Preferably, step of the present invention (2a) described buffered soln is phosphate buffer soln, preferred pH is 6.8-7, concentration is the phosphate buffer soln of 0.04-0.05mol/L, the pH of such as phosphoric acid buffer is 6.81,6.87,6.90,6.96 etc., and concentration is 0.041mol/L, 0.044mol/L, 0.046mol/L, 0.048mol/L etc.
Step of the present invention (2a) described buffered soln particularly preferably pH is 7, and concentration is the phosphate buffer soln of 0.05mol/L.
Preferably, in step of the present invention (2a) described buffered soln, the adding proportion of lipase is in every 100mL buffered soln, add 600-1000mg lipase, such as, in every 100mL buffered soln, the amount of adding lipase is 605mg, 624mg, 654mg, 680mg, 699mg, 715mg, 750mg, 785mg, 830mg, 860mg, 885mg, 914mg, 945mg, 987mg etc., preferably in every 100mL buffered soln, add 800mg lipase.When in every 100mL buffered soln, when adding the amount < 600mg of lipase, the catalytic efficiency of immobilized lipase-catalyzed dose that obtains is low, and reusing is also bad; And when in every 100mL buffered soln, when adding the amount > 1000mg of lipase, lipase easily runs off, and immobilized instability, cause waste.
Preferably, step (2a) described mixing is from the combination of centrifugal mixing, concussion mixing or any a kind or at least 2 kinds in being uniformly mixed, preferred centrifugal mixing, preferred centrifugal mixing under the condition of 2000-3000r/min further, the rotating speed of such as centrifugal mixing is 2100r/min, 2500r/min, 2700r/min, 2900r/min etc., particularly preferably in mixing centrifugal under the condition of 2400r/min.
Preferably, the add-on of step (2b) described sepiolite is the sepiolite that every 100mL lipase solution adds the sour modification that 3-7g step (1) obtains, and the quality that such as every 100mL lipase solution adds the sepiolite of the sour modification that step (1) obtains is 3.2g, 4.1g, 4.9g, 5.8g, 6.2g, 6.8g etc.; Preferably every 100mL lipase solution adds the sepiolite of the sour modification that 4g step (1) obtains.
Preferably, step (2b) described mixing is selected from the combination of centrifugal mixing, concussion mixing or any a kind or at least 2 kinds in being uniformly mixed, and mixed/stirred mixing etc. is such as shaken in described combination, preferably shakes mixing.
Preferably, the time of the described immobilized reaction of step (2b) is 5-9h, such as 5.2h, 5.8h, 6.3h, 6.9h, 7.5h, 8.1h, 8.8h etc., preferred 5-7h, further preferred 6h.
Preferably, step (2c) described cleaning is for using buffer solution for cleaning, and described damping fluid can be identical with the damping fluid in step (2a), also can be different from the damping fluid in step (2a), and the present invention does not limit; Preferably identical with the damping fluid in step (2a), namely use step (2a) described damping fluid to rinse.
Same, the operational condition of the supported step of lipase of the present invention and each step, be not limited in above-mentioned condition, above-mentioned each operation is optimum condition of the present invention and step, can meet and immobilized for the lipase experiment condition on the sepiolite of sepiolite or sour modification all be can be used for the present invention.
As a preferred embodiment of the present invention, the lipase described in step of the present invention (2) is immobilized to be comprised the steps:
400mg lipase to be dissolved in 50mL concentration be 0.05mol/L, pH is in the phosphate buffer soln of 7, carries out centrifugal under the condition of 2400r/min; Get 100mL enzyme liquid, add the sepiolite carrier of 4g modification; At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, preserve under normal temperature after drying.
In the preferred embodiment, " in a large number " in last described " filtering by a large amount of buffer solution for cleaning ", although be not an amount determined, but the object of cleaning step be by after reaction for immobilized residual fat enzyme on sepiolite or other impurity wash down, it is the operation that those skilled in the art can understand completely, also assurance can be known for " in a large number ", do not do concrete restriction herein, typical but non-limiting example have the quality of the damping fluid of described cleaning be the 10-50 of sepiolite quality doubly, 10-30 doubly, 20-60 doubly etc.
Three of object of the present invention is to provide a kind of enzyme catalysis method to prepare the method for biofuel.
Enzyme catalysis method prepares the method for biofuel, and certain research has been done in this area.At present, process for preparing biodiesel by enzyme generally uses immobilized lipase interval catalysis grease biodiesel synthesis, and key step is exactly by methyl alcohol and vegetables oil mixing, under existing at lipase-catalyzed dose, react, wherein methyl alcohol divides three times to add in reaction, prepare biofuel.The feature that enzyme catalysis method provided by the invention prepares the method for biofuel is: select immobilized on sepiolite lipase-catalyzed dose as catalyzer, carry out catalysis to the reaction of methyl alcohol and vegetables oil; Preferably with immobilized on the sepiolite of sour modification lipase-catalyzed dose as catalyzer, catalysis is carried out to the reaction of methyl alcohol and vegetables oil.
Preferably, describedly prepare in the method for biofuel at enzyme catalysis method, with the quality of vegetables oil for 100wt% calculates, the immobilized consumption of lipase-catalyzed dose on sepiolite is 0.8-10wt%, such as 0.88wt%, 0.95wt%, 1.42wt%, 1.89wt%, 2.03wt%, 2.7wt%, 4.5wt%, 6.8wt%, 7.5wt%, 8.41wt%, 9.24wt%, 9.7wt% etc., preferred 1-8wt%.
Prepare in the process of biofuel about enzyme catalysis method of the present invention, raw materials is well-known to those skilled in the art, and typical but non-limiting example has the combination of any a kind or at least 2 kinds in soybean oil, rapeseed oil, Viscotrol C, peanut oil, Semen Maydis oil or waste oil.
Preferably, the method that enzyme catalysis method of the present invention prepares biofuel comprises the steps:
(I) in reaction vessel, add immobilized lipase-catalyzed dose described in vegetables oil, methyl alcohol and claim 1 or 2;
(II) enzymic catalytic reaction is carried out;
(III), after step (II) terminates, suction filtration reclaims lipase; Filtrate is distilled, and reclaim methyl alcohol, remainder separatory leaches glycerine, and that is finally left is biofuel.
Wherein, preferably, the mol ratio that step (I) described vegetables oil and methyl alcohol add total amount is 1:2-1:5, such as 1:2.2,1:2.9,1:3.1,1:3.7,1:4,1:4.5,1:4.9 etc., preferred 1:3; Described methyl alcohol preferably divides three times and adds reaction vessel, and adding frequency is that every 22-26h adds 1 time, and such as every 22.5h adds 1 time, adds 3 times altogether; Preferably every 24h adds once; Every 23.2h adds 1 time, adds 3 times altogether; Preferably every 24h adds once; Every 24.5h adds 1 time, adds 3 times altogether; Every 25.8h adds 1 time, adds 3 times altogether; Preferably every 24h adds once.
In the present invention, what vegetables oil and methyl alcohol added the mol ratio of total amount is calculated as technical ability well-known to those skilled in the art, and calculation procedure is: (molecular-weight average of the quality/vegetables oil of vegetables oil): (molecular weight of the quality/methyl alcohol of methyl alcohol).Wherein, the molecular weight of methyl alcohol is 32.04, and the quality of methyl alcohol can directly weigh; The quality of vegetables oil also can obtain by directly weighing, and the molecular-weight average of vegetables oil can be calculated by saponification value (SV) and acid number (AV), the mensuration of saponification value can refer to GB-9104.2-88, and the mensuration of acid number can refer to GB9104.3-88, and the calculating formula of molecular-weight average is:
M=(56.1×1000×3)/(SV-AV)；
About the calculating of the molecular-weight average of vegetables oil, a lot of existing document also has and relates to, and those skilled in the art can consult voluntarily, such as document " preparation of biodiesel with vegetable oils, Wu Guoying, Jiangsu Petrochemical Engineering College journal; in September, 2002,14(3): 8-11 ".
Typical but non-limiting example has: for soybean oil, and it is considered herein that molecular-weight average is 880, then the calculating formula of the mol ratio of 100g soybean oil and 10g methyl alcohol is (100/880): (10/32.04); And for hogwash fat, it is considered herein that the molecular weight of hogwash fat is 920.
Preferably, step of the present invention (II) described temperature of reaction 30-40 DEG C, such as 31 DEG C, 33 DEG C, 36.3 DEG C, 37 DEG C, 39 DEG C, 39.5 DEG C etc.; Total reaction time 66-78h, preferably 72 hours.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention adopts the immobilized lipase of sepiolite, and the immobilized lipase of sepiolite especially adopting acid modified is as catalyzer, and the consumption of lipase-catalyzed dose is few; Reaction terminates latter immobilized lipase-catalyzed dose and can reuse, and recycling number of times is up to 10 times, although the activity of immobilized lipase-catalyzed dose slightly declines, vegetable oil conversion is that the transformation efficiency of biofuel still can reach more than 90%.
2, through supported lipase, acid-proof alkaline and resistance toheat comparatively protoenzyme significantly improve; Its optimal pH becomes 5.6 from 7.5, and optimum temperuture becomes 35 DEG C from 30 DEG C.
3, for the immobilized lipase of acid-treated sepiolite, better than the immobilized lipase effect of sepiolite of no process on hydrolysis rate.
4, the preparation method of biofuel provided by the invention, reactive behavior is high, and speed of response is fast, and reaction conditions is relatively gentle, can carry out, thus can reduce energy consumption of reaction, reduce costs under normal pressure and relatively low temperature; Reaction is carried out at ambient pressure, reduces the requirement to reaction unit, and catalyzer non-corrosiveness, the corrosion-resistant requirement of the equipment that also reduces, expense of reducing investment outlay.
5, immobilized lipase-catalyzed dose of catalyst stability provided by the invention is good, and consumption is few, and catalyzer can recirculation use, production process environmental friendliness; Working method is simple, and easy handling, the reaction times is short, and yield is high little to equipment corrosion, both can reduce the energy, can reduce costs again.
Embodiment
The interval value that the present invention provides, the not accurate end value of mathematical concept, and test and Selection has association when interval, suitably departs from end value and not cannot.
Below in conjunction with several specific embodiments; exemplary illustration and help understand the present invention further; but embodiment detail is only in order to the present invention is described; do not represent the present invention and conceive lower whole technical scheme; therefore should not be construed as the technical scheme total to the present invention to limit, some are In the view of technician, and the unsubstantiality not departing from inventive concept is changed; such as simply change with the technical characteristic with same or similar technique effect or replace, all belonging to scope.
Lipase described in the embodiment of the present invention is SUKALIP lipase, purchased from Su Kehan (Weifang) biotechnology company limited.Lipase of the present invention is not limited to SUKALIP lipase, and the lipase in the existing or new technology of any one all can be used for the present invention.
Embodiment 1:
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 30 DEG C of temperature, in 10g sepiolite, add the hydrochloric acid that 100mL concentration is 0.4mol/L, soak 12h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
A, be dissolved in 50mL phosphate buffer soln (0.05mol/L, pH7) by 400mg lipase, centrifugal (2400r/min), gets 100mL enzyme liquid; Add the sepiolite carrier of modification in 4g step (1); At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, after drying, obtain immobilized lipase.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add soybean oil and methyl alcohol (mol ratio 1:3), methyl alcohol divides three times and adds, add the immobilized lipase of sour modified meerschaum prepared, add-on be 3w%(in the quality of soybean oil for 100w%), react 72 hours at 35 DEG C, the transformation efficiency of product can reach 96.1%.
Embodiment 2:
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 30 DEG C of temperature, in 10g sepiolite, add the hydrochloric acid that 150mL concentration is 0.4mol/L, soak 12h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
400mg lipase is dissolved in 50mL phosphate buffer soln (0.05mol/L, pH7), centrifugal (2400r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 4g step (1); At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add rapeseed oil and methyl alcohol (mol ratio 1:3), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 3w%(in the quality of rapeseed oil for 100w%), react 72 hours at 30 DEG C, product yield reaches 95.7%.
Embodiment 3:
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 50 DEG C of temperature, in 10g sepiolite, add the hydrochloric acid that 200mL concentration is 1.2mol/L, soak 12h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
400mg lipase is dissolved in 50mL phosphate buffer soln (0.05mol/L, pH7), centrifugal (2400r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 4g step (1); At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add Viscotrol C and methyl alcohol (mol ratio 1:3), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 4w%(in the quality of Viscotrol C for 100w%), react 72 hours at 40 DEG C, product yield reaches 95.3%.
Embodiment 4:
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 50 DEG C of temperature, in 10g sepiolite, add the hydrochloric acid that 250mL concentration is 1.2mol/L, soak 18h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
400mg lipase is dissolved in 50mL phosphate buffer soln (0.05mol/L, pH7), centrifugal (2400r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 4g step (1); At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add Semen Maydis oil and methyl alcohol (mol ratio 1:3), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 8w%(in the quality of Semen Maydis oil for 100w%), react 72 hours at 35 DEG C, product yield reaches 96.5%.
Embodiment 5:
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 70 DEG C of temperature, in 10g sepiolite, add the hydrochloric acid that 150mL concentration is 2.0mol/L, soak 18h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
400mg lipase is dissolved in 50mL phosphate buffer soln (0.05mol/L, pH7), centrifugal (2400r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 4g step (1); At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add peanut oil and methyl alcohol (molar mass is than 1:3), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 8w%(in the quality of peanut oil for 100w%), when reacting little 72 at 30 DEG C, product yield reaches 97.5%.
Embodiment 6
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 70 DEG C of temperature, in 10g sepiolite, add the hydrochloric acid that 150mL concentration is 2.8mol/L, soak 18h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
400mg lipase is dissolved in 50mL phosphate buffer soln (0.05mol/L, pH7), centrifugal (2400r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 4g step (1); At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add the hogwash fat after refinement treatment and methyl alcohol (mol ratio 1:3), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 6w%(in the quality of hogwash fat for 100w%), react 72 hours at 30 DEG C, product yield reaches 97.2% respectively.
Embodiment 7
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 70 DEG C of temperature, in 10g sepiolite, add the hydrochloric acid that 250mL concentration is 2.0mol/L, soak 18h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
400mg lipase is dissolved in 50mL phosphate buffer soln (0.05mol/L, pH7), centrifugal (2400r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 4g step (1); At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add rapeseed oil and methyl alcohol (mol ratio 1:3), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 6w%(in the quality of rapeseed oil for 100w%), react 72 hours at 35 DEG C, product yield is respectively 95.9%.
Embodiment 8:
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 90 DEG C of temperature, in 10g sepiolite, add the hydrochloric acid that 250mL concentration is 2.8mol/L, soak 30h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
400mg lipase is dissolved in 50mL phosphate buffer soln (0.05mol/L, pH7), centrifugal (2400r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 4g step (1); At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add Viscotrol C and methyl alcohol (mol ratio 1:3), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 6w%(in the quality of Viscotrol C for 100w%), react 72 hours at 30 DEG C, product yield is respectively 96.7%.
Embodiment 9:
Investigate the repeated experiment result of immobilized lipase-catalyzed dose of sour modified meerschaum,
Except for the following differences, all the other are identical with above-mentioned example 1: investigate catalyzer repeated experiment result,
Catalyzer 1
Step (1a): the quality (g) of sepiolite and the ratio 1:10 of hydrochloric acid add-on (mL) at 30 DEG C, concentration is 0.4mol/L hydrochloric Acid Modification 12h;
Catalyzer 1 is repeated catalysis soybean oil and methyl alcohol, and the transformation efficiency of its product is followed successively by 95.2%, 94.3%, 94.4%, 94.3%, 93.2%, 92.7%, 92.8%, 90.6%, 90.0%, 90.1%;
Catalyzer 2
Step (1a): the quality (g) of sepiolite and the ratio 1:25 of hydrochloric acid add-on (mL) at 90 DEG C, concentration is 2.8mol/L hydrochloric Acid Modification 30h;
Catalyzer 2 is repeated catalysis soybean oil and methyl alcohol, and the transformation efficiency of its product is followed successively by 95.7%, 95.3%, 96.4%, 95.3%, 94.6%, 92.2%, 92.1%, 90.8%, 90.1%, 90.0%.
This shows, immobilized lipase provided by the present invention is through 10 repeated catalysis soybean oil and methyl alcohol, and the transformation efficiency of its product still can reach more than 90%.
Embodiment 10
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 82 DEG C of temperature, in 10g sepiolite, add the nitric acid that 80mL concentration is 6mol/L, soak 21h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 220 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
300mg lipase is dissolved in 50mL phosphate buffer soln (0.04mol/L, pH6.8), centrifugal (2000r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 7g step (1); At room temperature oscillation mixture; After reaction 5h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add Viscotrol C and methyl alcohol (mol ratio 1:2), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 0.8w%(in the quality of Viscotrol C for 100w%), react 66 hours at 40 DEG C, product yield is respectively 97.1%.
Embodiment 11
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) hydrochloric Acid Modification sepiolite:
A, at 73 DEG C of temperature, in 10g sepiolite, add the sulfuric acid that 700mL concentration is 0.1mol/L, soak 16.5h;
B, use distilled water wash, filter, dry, pulverize, high temperature sintering at 280 DEG C, obtains the sepiolite after hydrochloric Acid Modification.
(2) lipase is immobilized:
500mg lipase is dissolved in 50mL phosphate buffer soln (0.043mol/L, pH6.9), centrifugal (3000r/min), gets 100mL enzyme liquid, add the sepiolite carrier of modification in 3g step (1); At room temperature oscillation mixture; After reaction 9h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(3) in 0.25L reactor, add Viscotrol C and methyl alcohol (mol ratio 1:5), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 10w%(in the quality of Viscotrol C for 100w%), react 78 hours at 30 DEG C, product yield is respectively 98.5%.
Embodiment 12
The preparation method of immobilized lipase-catalyzed dose, comprises the steps:
(1) lipase is immobilized:
500mg lipase is dissolved in 50mL phosphate buffer soln (0.043mol/L, pH6.9), centrifugal (3000r/min), gets 100mL enzyme liquid, add 3g sepiolite carrier; At room temperature oscillation mixture; After reaction 9h, filter by a large amount of buffer solution for cleaning, being fixed lipase after drying.
Utilize the immobilized lipase-catalyzed dose of preparation biofuel prepared:
(2) in 0.25L reactor, add Viscotrol C and methyl alcohol (mol ratio 1:5), methyl alcohol divides three times and adds, above-mentioned immobilized lipase add-on be 10w%(in the quality of Viscotrol C for 100w%), react 78 hours at 30 DEG C, product yield is respectively 72.5%.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (41)
1. prepare immobilized lipase-catalyzed dose of biofuel for one kind, it is characterized in that, described catalyzer be by immobilized for lipase on sepiolite; Described sepiolite is the sepiolite of sour modification;
Described catalyzer is adopted and is prepared with the following method:
(1) sour modification is carried out to sepiolite;
(2) by the sepiolite after immobilized for the lipase sour modification obtained in step (1);
Wherein, sour modification carried out to sepiolite comprise the steps: described in step (1)
(1a) sepiolite is placed in acid to soak;
(1b) by the sepiolite washing after immersion, filter, dry, pulverize, calcination;
The concentration of step (1a) described acid is 0.1-6mol/L; Described sepiolite is the acid that every gram of sepiolite adds 8-70mL with the ratio of acid;
Wherein, the lipase described in step (2) is immobilized to be comprised the steps:
(2a) lipase is dissolved in buffered soln, mixing, obtains lipase solution;
(2b) in lipase solution, add the sepiolite of the sour modification that step (1) obtains, mixing, carries out immobilized reaction;
(2c) reaction product is cleaned, filter, dry, obtain immobilized immobilized lipase on sepiolite; The immobilized lipase normal temperature of gained is preserved;
In step (2a) described buffered soln, the adding proportion of lipase is in every 100mL buffered soln, adds 600-1000mg lipase; Step (2a) described buffered soln is pH is 6.8-7, and concentration is the phosphate buffer soln of 0.04-0.05mol/L.
2. immobilized lipase-catalyzed dose as claimed in claim 1, it is characterized in that, described acid is selected from the combination of any a kind or at least 2 kinds in hydrochloric acid, sulfuric acid or nitric acid.
3. immobilized lipase-catalyzed dose as claimed in claim 1, it is characterized in that, described acid is hydrochloric acid and/or sulfuric acid.
4. immobilized lipase-catalyzed dose as claimed in claim 1, it is characterized in that, described acid is hydrochloric acid.
5. the preparation method of immobilized lipase-catalyzed dose as described in one of Claims 1 to 4, is characterized in that, described method comprises the steps:
(1) sour modification is carried out to sepiolite;
(2) by the sepiolite after immobilized for the lipase sour modification obtained in step (1);
Wherein, sour modification carried out to sepiolite comprise the steps: described in step (1)
(1a) sepiolite is placed in acid to soak;
(1b) by the sepiolite washing after immersion, filter, dry, pulverize, calcination;
The concentration of step (1a) described acid is 0.1-6mol/L; Described sepiolite is the acid that every gram of sepiolite adds 8-70mL with the ratio of acid;
Wherein, the lipase described in step (2) is immobilized to be comprised the steps:
(2a) lipase is dissolved in buffered soln, mixing, obtains lipase solution;
(2b) in lipase solution, add the sepiolite of the sour modification that step (1) obtains, mixing, carries out immobilized reaction;
(2c) reaction product is cleaned, filter, dry, obtain immobilized immobilized lipase on sepiolite; The immobilized lipase normal temperature of gained is preserved;
In step (2a) described buffered soln, the adding proportion of lipase is in every 100mL buffered soln, adds 600-1000mg lipase; Step (2a) described buffered soln is pH is 6.8-7, and concentration is the phosphate buffer soln of 0.04-0.05mol/L.
6. preparation method as claimed in claim 5, is characterized in that, step (1a) described acid is selected from the combination of any a kind or at least 2 kinds in hydrochloric acid, sulfuric acid or nitric acid.
7. preparation method as claimed in claim 5, it is characterized in that, step (1a) described acid is hydrochloric acid and/or sulfuric acid.
8. preparation method as claimed in claim 5, it is characterized in that, step (1a) described acid is hydrochloric acid.
9. preparation method as claimed in claim 5, it is characterized in that, the concentration of step (1a) described acid is 0.4-2.8mol/L.
10. preparation method as claimed in claim 5, it is characterized in that, step (1a) described acid is the hydrochloric acid of 0.4-2.8mol/L.
11. preparation methods as claimed in claim 5, is characterized in that, step (1a) described sepiolite is the acid that every gram of sepiolite adds 10-25mL with the ratio of acid.
12. preparation methods as claimed in claim 5, it is characterized in that, step (1a) described soaking temperature is 30-90 DEG C; Described soak time is 12-30h.
13. preparation methods as claimed in claim 5, it is characterized in that, step (1a) described soaking temperature is 35-75 DEG C; Described soak time is 13-25h.
14. preparation methods as claimed in claim 5, it is characterized in that, step (1b) described washing is for washing with water, and described wet concentration is from deionized water and/or distilled water; Described calcination temperature is 220-280 DEG C.
15. preparation methods as claimed in claim 5, it is characterized in that, step (1b) described calcination temperature is 230-250 DEG C.
16. preparation methods as claimed in claim 5, it is characterized in that, step (1b) described calcination temperature is 240 DEG C.
17. preparation methods as described in one of claim 5 ~ 16, is characterized in that, carrying out sour modification to sepiolite and comprise the steps: described in step (1)
At 30-90 DEG C, add the hydrochloric acid that concentration is 0.4 ~ 2.8mol/L in sepiolite, hydrochloric acid add-on is 10-25mL/ every gram sepiolite, soaks 12-30h; Then use distilled water wash, filter, dry, pulverize, high temperature sintering at 240 DEG C, obtain the sepiolite that acid is modified.
18. preparation methods as claimed in claim 5, is characterized in that, step (2a) described buffered soln is pH is 7, and concentration is the phosphate buffer soln of 0.05mol/L.
19. preparation methods as claimed in claim 5, is characterized in that, in step (2a) described buffered soln, the adding proportion of lipase is in every 100mL buffered soln, add 800mg lipase.
20. preparation methods as claimed in claim 5, is characterized in that, step (2a) described mixing is selected from the combination of centrifugal mixing, concussion mixing or any a kind or at least 2 kinds in being uniformly mixed.
21. preparation methods as claimed in claim 5, is characterized in that, be mixed into centrifugal mixing described in step (2a).
22. preparation methods as claimed in claim 5, is characterized in that, be mixed into centrifugal mixing under the condition of 2000-3000r/min described in step (2a).
23. preparation methods as claimed in claim 5, is characterized in that, be mixed into centrifugal mixing under the condition of 2400r/min described in step (2a).
24. preparation methods as claimed in claim 5, is characterized in that, the add-on of step (2b) described sepiolite is the sepiolite that every 100mL lipase solution adds the sour modification that 3-7g step (1) obtains.
25. preparation methods as claimed in claim 5, is characterized in that, the add-on of step (2b) described sepiolite is the sepiolite that every 100mL lipase solution adds the sour modification that 4g step (1) obtains.
26. preparation methods as claimed in claim 5, is characterized in that, step (2b) described mixing is selected from the combination of centrifugal mixing, concussion mixing or any a kind or at least 2 kinds in being uniformly mixed.
27. preparation methods as claimed in claim 5, is characterized in that, step (2b) described mixing is selected from concussion mixing.
28. preparation methods as claimed in claim 5, is characterized in that, the time of the described immobilized reaction of step (2b) is 5-9h.
29. preparation methods as claimed in claim 5, is characterized in that, the time of the described immobilized reaction of step (2b) is 5-7h.
30. preparation methods as claimed in claim 5, is characterized in that, the time of the described immobilized reaction of step (2b) is 6h.
31. preparation methods as claimed in claim 5, it is characterized in that, step (2c) described cleaning is for using buffer solution for cleaning.
32. preparation methods as claimed in claim 5, it is characterized in that, step (2c) described cleaning is for rinse with step (2a) described damping fluid.
33. preparation methods as claimed in claim 5, is characterized in that, the lipase described in step (2) is immobilized to be comprised the steps:
400mg lipase to be dissolved in 50mL concentration be 0.05mol/L, pH is in the phosphate buffer soln of 7, carries out centrifugal under the condition of 2400r/min; Get 100mL enzyme liquid, add the sepiolite carrier of 4g modification; At room temperature oscillation mixture; After reaction 6h, filter by a large amount of buffer solution for cleaning, preserve under normal temperature after drying.
34. 1 kinds of enzyme catalysis methods prepare the method for biofuel, for methyl alcohol and vegetables oil react under lipase-catalyzed dose of existence, preparation biofuel, is characterized in that, described lipase-catalyzed dose is on sepiolite lipase-catalyzed dose of immobilized as described in one of Claims 1 to 4.
35. methods as claimed in claim 34, is characterized in that, described lipase-catalyzed dose is on the sepiolite of sour modification lipase-catalyzed dose of immobilized as described in one of claim 2 ~ 4.
36. methods as claimed in claim 35, is characterized in that, in described method, with the quality of vegetables oil for 100wt% calculates, the immobilized consumption of lipase-catalyzed dose on sepiolite is 0.8-10wt%.
37. methods as claimed in claim 34, is characterized in that, in described method, with the quality of vegetables oil for 100wt% calculates, the immobilized consumption of lipase-catalyzed dose on sepiolite is 1 ~ 8wt%.
38. methods as claimed in claim 34, it is characterized in that, described method comprises the steps:
(I) in reaction vessel, add immobilized lipase-catalyzed dose described in vegetables oil, methyl alcohol and claim 1 or 2;
(II) enzymic catalytic reaction is carried out;
(III), after step (II) terminates, suction filtration reclaims lipase; Filtrate is distilled, and reclaim methyl alcohol, remainder separatory leaches glycerine, and that is finally left is biofuel;
Wherein, step (I) described vegetables oil and methyl alcohol add the mol ratio of total amount is 1:2-1:5; Described methyl alcohol divides three times and adds reaction vessel, and adding frequency is that every 22-26h adds 1 time.
39. methods as claimed in claim 38, is characterized in that, the mol ratio that step (I) described vegetables oil and methyl alcohol add total amount is 1:3; Described methyl alcohol divides three times and adds reaction vessel, and adding frequency is that every 24h adds once.
40. methods as claimed in claim 38, is characterized in that, step (II) described temperature of reaction 30-40 DEG C; Total reaction time 66-78h.
41. methods as claimed in claim 38, is characterized in that, step (II) described temperature of reaction 30-40 DEG C; Total reaction time 72 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210309958.XA CN102827825B (en) | 2012-08-28 | 2012-08-28 | Immobilized lipase catalyst for preparing biodiesel and application of immobilized lipase catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210309958.XA CN102827825B (en) | 2012-08-28 | 2012-08-28 | Immobilized lipase catalyst for preparing biodiesel and application of immobilized lipase catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102827825A CN102827825A (en) | 2012-12-19 |
| CN102827825B true CN102827825B (en) | 2015-06-10 |
Family
ID=47331138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210309958.XA Expired - Fee Related CN102827825B (en) | 2012-08-28 | 2012-08-28 | Immobilized lipase catalyst for preparing biodiesel and application of immobilized lipase catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102827825B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107586770A (en) * | 2017-08-23 | 2018-01-16 | 吉林大学 | A kind of porcine pancreatic lipase inorganic hybrid nano flower catalyst, preparation method and its application in biodiesel preparation |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104353445A (en) * | 2014-10-31 | 2015-02-18 | 华南理工大学 | Solid base catalyst for preparing biodiesel and preparation method and application of solid base catalyst |
| CN105274157B (en) * | 2015-12-01 | 2018-07-20 | 河北工业大学 | A kind of method of static state emulsion method immobilized lipase production biodiesel |
| CN108187649A (en) * | 2017-12-28 | 2018-06-22 | 合肥小小作为信息科技有限公司 | A kind of processing method of tail gas catalyzed agent carrier newly developed |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367035A (en) * | 2001-01-22 | 2002-09-04 | 王福生 | Sepiolite type natural mineral series active drying agent and its production process |
| CN100375781C (en) * | 2005-11-09 | 2008-03-19 | 中国科学院广州能源研究所 | Production of biological diesel oil by fixed enzyme method |
| CN102505008B (en) * | 2011-11-09 | 2014-06-11 | 华南理工大学 | Magnetic immobilized cross-linked lipase aggregate and preparation method and application thereof |
-
2012
- 2012-08-28 CN CN201210309958.XA patent/CN102827825B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107586770A (en) * | 2017-08-23 | 2018-01-16 | 吉林大学 | A kind of porcine pancreatic lipase inorganic hybrid nano flower catalyst, preparation method and its application in biodiesel preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102827825A (en) | 2012-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ganesan et al. | An overview on the recent advances in the transesterification of vegetable oils for biodiesel production using chemical and biocatalysts | |
| CN102827825B (en) | Immobilized lipase catalyst for preparing biodiesel and application of immobilized lipase catalyst | |
| JP5964327B2 (en) | Improved process for producing fatty acid alkyl esters (biodiesel) from triglyceride oils by using environmentally friendly solid base catalysts | |
| CN103710158B (en) | Method for producing biodiesel by using kitchen wastes | |
| Basumatary et al. | Advances in CaO-based catalysts for sustainable biodiesel synthesis | |
| CN109603843A (en) | A kind of core-shell catalyst and preparation method thereof and the application in reformation hydrogen production | |
| CN101205473B (en) | Catalyzed preparation of biodiesel by calcining sodium silicate | |
| CN103614155A (en) | Preparation method for hydrocarbon fuels from algae oil | |
| CN111205931A (en) | Method for catalytically synthesizing biodiesel by using roasted Ca-Al hydrotalcite | |
| CN105688965B (en) | Mesoporous niobium pentaoxide/nitrogen-doped graphene high-efficiency composite photocatalyst preparation method | |
| CN101294093B (en) | Integrated preparation method for biological diesel oil and isolated plant | |
| CN100515559C (en) | Catalyst for generating biological diesel oil and catalystic pyrolysis for producing biological diesel oil | |
| CN101780415A (en) | Coal cinder supported solid base catalyst and preparation method and use thereof | |
| CN107488519A (en) | A kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal | |
| CN102492559A (en) | Method for preparing biodiesel in novel alkaline ionic liquid | |
| CN100999680A (en) | Esterification reaction tech. of preparing biodiesel by waste oil | |
| CN100348314C (en) | Synthesis reaction catalyst for loading type alkali metal biodiesel oil | |
| CN100551562C (en) | A kind of method that adopts the nanocatalyst catalytically liquefying biomass | |
| CN110773229B (en) | Polyacrylic acid modified SiO for catalyzing sodium borohydride to hydrolyze to prepare hydrogen2Method for producing particles | |
| Ingle et al. | Nanocatalysts in biodiesel production | |
| CN102247888A (en) | Preparation method for granular carbon-based solid acid catalyst for producing biological diesel oil | |
| CN112156767A (en) | Wollastonite loaded strontium and lanthanum solid base catalyst, and preparation method and application thereof | |
| CN110437892A (en) | A kind of biodiesel preparation process | |
| CN106381230A (en) | Modification method of low-NOX-emission biodiesel | |
| CN102078825B (en) | Solid catalyst for preparing biodiesel by utilizing normal-pressure ester exchange method and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150610 Termination date: 20160828 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |